CN109294208A - Photochromic urethane composition and its preparation method and application, the color-changing lens comprising it - Google Patents
Photochromic urethane composition and its preparation method and application, the color-changing lens comprising it Download PDFInfo
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- CN109294208A CN109294208A CN201811162285.3A CN201811162285A CN109294208A CN 109294208 A CN109294208 A CN 109294208A CN 201811162285 A CN201811162285 A CN 201811162285A CN 109294208 A CN109294208 A CN 109294208A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
- G02C7/102—Photochromic filters
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Abstract
The present invention provides a kind of photochromic urethane composition and preparation method thereof, comprising its color-change resin eyeglass, the urethane composition includes following component in parts by weight: urethane raw 955-965 parts by weight；Change colour liquid 15-25 parts by weight；Dispersion resin 18-22 parts by weight；Initiator 0.3-0.5 parts by weight.The present invention selects discoloration liquid and dispersion resin to be added in urethane raw, dispersion resin can promote fine dispersion of the liquid in urethane composition that change colour, keep photochromic composition color changeable effect provided by the invention good, and when composition is used for color-changing lens, it can be ensured that color-changing lens discoloration is uniform.
Description
Technical field
The invention belongs to photochromic material field, be related to a kind of photochromic urethane composition and preparation method thereof and
Using, include its color-changing lens.
Background technique
Ultraviolet range accounts for the 7% of total solar radiation energy, and excessive ultraviolet light can cause photochemical reaction, especially to people
Skin, eyes and immune system of body etc. cause damages, it should be noted that protection, therefore, being engaged in outdoor activity person will avoid growing
Time is exposed to the sun in the sunlight.Eyes are the positions most sensitive to ultraviolet light, and ultraviolet light is long-term, is repeatedly exposed to the sun, and can cause acute knot
Film inflammation, retinal disease etc., light-sensitive sunglasses should be worn by being engaged in outdoor activity person.Since resin color-changing lens have unique light
Performance is learned, the eyeglass after outdoor discoloration can effectively filter harmful ultraviolet light and blue light, can restore normal again indoors
Colour of lens, therefore eyesight can be protected well, and there is light, impact resistance and the good characteristics such as non-friable；The eyeglass mesh
It is preceding rather well received, but there is also many deficiencies for current discoloration technique.
Currently, there are two types of technologies for manufacture resin chameleon glass block, one kind is incorporation formula, by photochromic dyes and eyeglass list
Body mixes, and the eyeglass with photochromic function is made by being heating and curing, but color-change powder and polymer are stirred
Cheng Zhong can be fallen, and since this technique is whole if dispersion or emulsifying bad in raw material filtering before curing by PP filter element filtering
A eyeglass is filled with the discoloration factor, and the color-changing lens uniform coloring worked it out is poor, and color change is slow under shortwave wavelength,
The depth that changes colour is poor, and resume speed is slower under indoor conditions, and it is not lasting to change colour；Another kind is surface-coating technology, this skill
Art changes colour, and depth is good, and discoloration rate is very fast, but for infiltration type technology, technique is relative complex, and eyeglass discoloration is held
Long property is poor.CN105892092A discloses a kind of resin color-changing lens structure, mainly includes preceding discoloration stiffening layer, discoloration adds afterwards
Hard formation, front and back antireflective combined films and waterproof membrane, the eyeglass discoloration finally obtained uniformly, scrubbing resistance, using permanent, but technique
Still more complex, it is equivalent to increase cost.CN104460040A discloses a kind of colouring method of color-changing lens, for using ultrasound
Wave cleans eyeglass-drying-pre-cooling-IPA cleaning-dip-coating electrochromic solution-prebake-stiffened heat cure again, this method on eyeglass
It overcomes discoloration in the prior art to be affected by temperature, when degree is higher, center and peripheral shade has certain color difference, discoloration
Occurs the problems such as centrifugal force generates striped when spin coating.
Currently, in the market photochromic mainly based on middle low-refraction eyeglass, for high luminosity consumer, folding
It is relatively low to penetrate rate, lens thickness is thick, highly inconvenient using meeting；And high refractive index color-changing lens in a manner of spin coating or immersion into
Row processing, needs special technique process and corresponding various equipment, so that cost is significantly increased, high price limits its consumption
Group.CN101838369A disclose it is a kind of manufacture chameleon glass block monomer composition and chameleon glass block preparation method,
Component and weight percent content include: (1) monomer mixture: (methyl) acrylic resin 40-70%, vinyl monomer 20-
40%, crosslinking agent 10-20%, auxiliary material and auxiliary agent used in (2) 1kg monomer mixture: chromotropic dye 0.1-1kg, ultraviolet radiation absorption
Agent 0.05-0.2g, antioxidant 2-6g, light stabilizer 2-6g, polymeric additive 1-5g, polymerization initiator 0.8-5g are obtained
Light-sensitive sunglasses refractive index is 1.60-1.63, but color-shifting colorant uniformity is poor, restores relatively slow under indoor conditions.
It needs to develop a kind of new high refractive index color-changing lens at present, preparation method is simple, save the cost and color-changing lens
Have many advantages, such as that color-shifting colorant uniformity is good, color changeable effect is good.
Summary of the invention
The purpose of the present invention is to provide a kind of photochromic urethane composition and its preparation method and application, include it
Color-changing lens, photochromic polyurethane provided by the invention has photochromic characteristic, and can be adapted for a variety of foldings
The eyeglass for penetrating rate can be applied to the photochromic layer of high refractive index color-changing lens, and preparation process is simple, carry out without special equipment
Production and processing.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the urethane composition is by weight the present invention provides a kind of photochromic urethane composition
Number includes following component:
The present invention selects discoloration liquid and dispersion resin to be added in urethane raw, and dispersion resin can promote to change colour liquid poly-
Fine dispersion in urethane composition keeps photochromic composition color changeable effect provided by the invention good, and when composition is used for
When color-changing lens, it can be ensured that color-changing lens discoloration is uniform.
In the present invention, the parts by weight of the urethane raw are 955-965 parts by weight, such as 956 parts by weight, 958
Parts by weight, 960 parts by weight, 961 parts by weight, 963 parts by weight etc..
In the present invention, the parts by weight of the discoloration liquid are 15-25 parts by weight, such as 16 parts by weight, 18 parts by weight, 20
Parts by weight, 21 parts by weight, 23 parts by weight etc..
In the present invention, the parts by weight of the dispersion resin be 18-22 parts by weight, such as 19 parts by weight, 20 parts by weight,
21 parts by weight etc..
In the present invention, the parts by weight of the initiator are 0.3-0.5 parts by weight, such as 0.4 parts by weight etc..
Preferably, the discoloration liquid is the mixed liquor of at least two color-change powders and isocyanates.
Preferably, the color-change powder is for selected from spiro-pyrans class color-change powder, spiral shell uh piperazine class color-change powder or diarylethene
At least two combination in color-change powder；
Preferably, the dispersion resin is polyol polyester, further preferred polyadipate 1,6- hexylene glycol esterdiol, poly-
Adipic acid methyl-1,3-propanediol 1,6-HD esterdiol, polyadipate 1,4- butanediol neopentyl glycol esterdiol gather oneself two
Acid methyl -1,3- propylene glycol ester glycol, polyadipate methyl-1,3-propanediol ester 1,4- butyl glycol ester diol and poly- sebacic acid 1,
In 6- glycol neopentyl glycol esterdiol any one or at least two combination.
The present invention selects highly viscous polyester polyol, itself contained ester group isopolarity group both can be with liquid
Each group of polyurethane, which combines, enhances its cohesive strength, can also reinforce adhesion strength with solid polyurethane carrier；Polyester polyols simultaneously
There is alcohol biggish intermolecular cohesive energy to have good crystallinity at the time of molding, ensure that discoloration composition disperses in carrier surface
Uniformity；And polyesterols itself have wearability, after in conjunction with its amino with polyurethane, further ensure that the strong of product
Degree and wearability.
When the discoloration liquid that the present invention selects is spiro-pyrans class color-change powder, spiral shell uh piperazine class color-change powder or diarylethene discoloration
When at least two combination in powder, discoloration liquid is not easy to be stabilized in urethane raw, when selecting polyol polyester conduct
When dispersing agent, the discoloration liquid that polyol polyester can be such that the present invention selects is stable in the presence of in urethane raw, it is ensured that discoloration liquid
It does not fail, and discoloration liquid can be made to be dispersed in urethane raw, it is ensured that the composition discoloration finally obtained is uniform.
In the present invention, the urethane raw includes following component in parts by weight:
Bicyclic [2.2.1] the heptane 480-530 parts by weight of 2,5 (or 2,6)-bis- (isocyanatomethyls)；
Four (3- mercaptopropionic acid) pentaerythritol ester 200-250 parts by weight；
The pungent two mercaptan 210-260 parts by weight of 4- thiopurine methyltransferase -3,6- dithia -1,8-.
In the present invention, described 2, the parts by weight of bicyclic [2.2.1] heptane of 5 (or 2,6)-bis- (isocyanatomethyls)
For 480-530 parts by weight, such as 490 parts by weight, 500 parts by weight, 510 parts by weight, 515 parts by weight, 520 parts by weight etc..
In the present invention, the parts by weight of described four (3- mercaptopropionic acid) pentaerythritol ester are 200-250 parts by weight, such as
210 parts by weight, 215 parts by weight, 220 parts by weight, 225 parts by weight, 230 parts by weight, 235 parts by weight, 240 parts by weight, 245 weight
Part etc..
In the present invention, the parts by weight of pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- are 210-260 weight
Measure part, such as 215 parts by weight, 220 parts by weight, 225 parts by weight, 230 parts by weight, 240 parts by weight, 245 parts by weight, 250 weight
Part, 255 parts by weight etc..
Preferably, the structural formula of the initiator is as follows:
RnSnX(4-n)；
Wherein, n is the integer of 1-4, such as 2,3 etc., R is alkyl or aromatic radical, and X is-F ,-Cl or-Br.
Preferably, the initiator is ethyl tin dichloride, dimethyl tin bibromide, dibutyl tin dichloride, front three
In base monochlor(in)ate tin or trimethyl monobromination tin any one or at least two combination.
Second aspect, the present invention provides the preparation method of photochromic urethane composition as described in relation to the first aspect,
The preparation method includes the following steps:
(1) the discoloration liquid of formula ratio, dispersion resin are mixed with some polyurethanes raw material, obtains the first mixed liquor；
(2) initiator is mixed with remainder urethane raw, obtains the second mixed liquor；
(3) the first mixed liquor and the second mixed liquor are mixed, filtering, obtains the photochromic urethane composition；
Preferably, the preparation method includes the following steps:
(A) the discoloration liquid of formula ratio, dispersion resin and 2,5 (or 2,6)-bis- (isocyanatomethyls) is bicyclic
Four (3- mercaptopropionic acid) pentaerythritol esters are added after the mixing of [2.2.1] heptane, obtain the first mixed liquor；
(B) initiator and pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- are mixed, obtains the second mixed liquor；
(C) the first mixed liquor and the second mixed liquor are mixed, filtering, obtains the photochromic urethane composition.
Preferably, during preparing the photochromic urethane composition, rate-determining steps (A)-(C) temperature is respectively
It is independently 10-15 DEG C, such as 11 DEG C, 12 DEG C, 13 DEG C, 14 DEG C etc..
Preferably, in step (A), four (3- mercaptopropionic acid) pentaerythritol esters are added under conditions of vacuum.
Preferably, step (B), (C) described mixing are to be stirred under vacuum mixing.
Preferably, before step (C) described filtering, first under the conditions of-(0.1-0.2) MPa (such as -0.12MPa, -
0.15MPa, -0.18MPa etc.) vacuumize 50-60min, such as 52min, 54min, 56min, 58min etc..
Preferably, step (C) filtering is carried out using the closed filter core of polytetrafluoroethylene (PTFE).
Preferably, the aperture of the filter core is 0.8-1.2 μm, such as 0.9 μm, 1.0 μm, 1.1 μm etc..
As the optimal technical scheme of preparation method, the preparation method includes the following steps:
(A) the discoloration liquid of formula ratio, dispersion resin and 2,5 (or 2,6)-bis- (isocyanatomethyls) is bicyclic
[2.2.1] heptane was added for four (3- mercaptopropionic acid) seasons penta in the case where 10-15 DEG C, vacuum stirring after mixing at 10-15 DEG C
Four alcohol esters obtain the first mixed liquor；
(B) by initiator and pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- the case where being stirred under vacuum in 10-15
It is mixed at DEG C, obtains the second mixed liquor；
(C) the first mixed liquor and the second mixed liquor are mixed at 10-15 DEG C the case where being stirred under vacuum, then-
It was carried out after vacuumizing 50-60min under the conditions of 0.1MPa using the closed filter core of polytetrafluoroethylene (PTFE) that aperture is 0.8-1.2 μm
Filter, obtains the photochromic urethane composition.
The third aspect, the present invention provides photochromic urethane compositions as described in relation to the first aspect in light-sensitive sunglasses
Application.
Composition provided by the invention has photochromic characteristic, and it is each to can be applied to light-sensitive sunglasses, photo chromic glass etc.
Kind needs to shield the place of ultraviolet light.
Fourth aspect, the present invention provides a kind of color-changing lens, the color-changing lens include mirror plate layers and photochromatic layer.
Mirror plate layers of the present invention be the semi-finished lenses with certain refractive index, it is current in the prior art, this
Kind eyeglass can be applied directly, directly apply after can also plating dura mater, plating anti-reflection film.
Preferably, the raw material for preparing of the photochromatic layer includes photochromic polyurethane composition described in first aspect
Object.
Preferably, the raw material for preparing of the photochromatic layer is photochromic urethane composition described in first aspect.
Preferably, the photochromatic layer with a thickness of 0.8-1.0mm, such as 0.9mm etc..
Preferably, the mirror plate layers are polyurethane mirror plate layers.
Preferably, the refractive index of the mirror plate layers be 1.553-1.74, such as 1.56,1.60,1.62,1.65,1.67,
1.70,1.72 etc..
Photochromic urethane composition provided by the invention not only can be applied to the lower eyeglass of refractive index, but also can answer
For the higher polyurethane eyeglass of refractive index.
Preferably, the color-changing lens further include hard membrane layer and antireflective coating.
Those skilled in the art know, when producing eyeglass at present, in order to increase the hardness and anti-reflection property of eyeglass, generally can
After the completion of eyeglass preparation, dura mater and anti-reflection film are plated.
5th aspect, the present invention provides the preparation method of the color-changing lens as described in fourth aspect, the preparation method
Include: to mold photochromatic layer mold and mirror plate layers, injects photochromic urethane composition described in first aspect, then
Solidification, obtains the color-changing lens.
Preferably, the diameter of the mirror plate layers is identical as the diameter of the photochromatic layer mold.
Preferably, the solidification carries out in the following manner:
One-step solidification is carried out first: being raised to temperature 30-35 DEG C (such as 32 DEG C, 34 DEG C etc.) from room temperature in 1h, is kept the temperature
5-5.5h (such as 5.2h, 5.4h etc.) is then warming up to 55-65 DEG C (such as 57 DEG C, 60 DEG C, 62 DEG C etc.) in 5h and keeps the temperature 3- afterwards
3.5h (such as 3.2h, 3.4h etc.) is then warming up to 85-95 DEG C (such as 87 DEG C, 90 DEG C, 92 DEG C etc.) and is warming up in 0.5h afterwards
100-105 DEG C (such as 102 DEG C, 104 DEG C etc.) is warming up to 120-130 DEG C of (such as 122 DEG C, 124 DEG C, 126 DEG C, 128 in 0.5h afterwards
DEG C etc.), temperature is reduced to 65-75 DEG C (such as 68 in 1h after keeping the temperature 2-2.5h (such as 2.2h, 2.4h etc.) at this temperature
DEG C, 70 DEG C, 72 DEG C etc.)；Be cleaned by ultrasonic after the completion of one-step solidification, then carried out at 130 DEG C secondary curing 2-2.5h (such as
2.2h, 2.4h etc.).
Preferably, the preparation method further includes plating dura mater, plating anti-reflection film after solidification.
Preferably, the method for the plating dura mater is dip coating.
Preferably, the method for the plating anti-reflection film is vacuum evaporatation.
Compared with the existing technology, the invention has the following advantages:
(1) present invention selects discoloration liquid and dispersion resin to be added in urethane raw, and dispersion resin can promote the liquid that changes colour
Fine dispersion in urethane composition keeps photochromic composition color changeable effect provided by the invention good, and works as composition
When for color-changing lens, it can be ensured that color-changing lens discoloration is uniform；
(2) when the discoloration liquid that the present invention selects is spiro-pyrans class color-change powder, spiral shell uh piperazine class color-change powder or diarylethene
When at least two combination in color-change powder, discoloration liquid is not easy to be stabilized in urethane raw, when selecting polyol polyester
When as dispersing agent, the discoloration liquid that polyol polyester can be such that the present invention selects is stable in the presence of in urethane raw, it is ensured that is become
Color liquid does not fail, and discoloration liquid can be made to be dispersed in urethane raw, it is ensured that the composition discoloration finally obtained is uniform；
(3) color-changing lens provided by the invention have the characteristics that photochromic, and color changeable effect is good, wherein color-changing lens
Transmitance for ultraviolet light is only 5-8%, it is possible to prevente effectively from filtering harmful ultraviolet light, protects eyesight well.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of color-changing lens, including mirror plate layers and photochromatic layer, preparation method include the following steps:
(1) 150g discoloration liquid, 200g dispersion resin and 4.85kg 2,5 (or 2,6)-bis- (isocyanatomethyls) is double
(3- mercaptopropionic acid) season penta of 2.2kg tetra- is added in the case where 10 DEG C, vacuum stirring after mixing at 10 DEG C in ring [2.2.1] heptane
Four alcohol esters obtain the first mixed liquor, wherein discoloration liquid is spiro-pyrans class color-change powder and spiral shell uh piperazine class color-change powder and isocyanates
Mixed liquor；
(2) by 5.0g initiator and pungent two mercaptan of 2.6kg 4- thiopurine methyltransferase -3,6- dithia -1,8- vacuum stirring feelings
Condition mixes at 10 DEG C, obtains the second mixed liquor, wherein initiator is Methylethyl stannous chloride；
(3) the first mixed liquor and the second mixed liquor are mixed at 10 DEG C the case where being stirred under vacuum, then in -0.1MPa
Under the conditions of vacuumize and be filtered using the closed filter core of polytetrafluoroethylene (PTFE) that aperture is 1.0 μm after 60min, obtain photochromic
Urethane composition；
(4) by mirror plate layers and photochromatic layer mold clamping, mirror plate layers and the spacing of photochromatic layer mold are when closing film
1.0mm injects photochromic urethane composition, temperature is then raised to 30 DEG C from room temperature in 1h, heat preservation 5h is then in 5h
3.5h is kept the temperature after being inside warming up to 55 DEG C, is warming up to 120 DEG C after being warming up to 100 DEG C in 0.5h after being then warming up to 85 DEG C in 0.5h,
Temperature is reduced to 65 DEG C in 1h after keeping the temperature 2.5h at this temperature；It is cleaned by ultrasonic after the completion of one-step solidification, then at 130 DEG C
Secondary curing 2h is carried out, plates dura mater using dip coating, vacuum evaporatation plates anti-reflection film, obtains color-changing lens.
Embodiment 2-3
Difference with embodiment 1 is only that in the present embodiment, the additive amount for the liquid that changes colour is 250g (embodiment 2), 200g
(embodiment 3).
Embodiment 4-5
Difference with embodiment 1 is only that, in the present embodiment, the additive amount of dispersion resin be 180g (embodiment 4),
220g (embodiment 5).
Embodiment 6
A kind of color-changing lens, including mirror plate layers and photochromatic layer, preparation method include the following steps:
(1) 150g discoloration liquid, 200g dispersion resin and 5.3kg 2,5 (or 2,6)-bis- (isocyanatomethyls) is bicyclic
2.2kg tetra- (3- mercaptopropionic acid) Ji Wusi is added in the case where 15 DEG C, vacuum stirring after mixing at 15 DEG C in [2.2.1] heptane
Alcohol ester obtains the first mixed liquor, wherein discoloration liquid is spiro-pyrans class color-change powder and diarylethene color-change powder and isocyanates
Mixed liquor；
(2) by 3.0g initiator and pungent two mercaptan of 2.15kg 4- thiopurine methyltransferase -3,6- dithia -1,8- in vacuum stirring
Situation mixes at 15 DEG C, obtains the second mixed liquor；
(3) the first mixed liquor and the second mixed liquor are mixed at 15 DEG C the case where being stirred under vacuum, then in -0.2MPa
Under the conditions of vacuumize and be filtered using the closed filter core of polytetrafluoroethylene (PTFE) that aperture is 0.8 μm after 50min, obtain photochromic
Urethane composition；
(4) by mirror plate layers and photochromatic layer mold clamping, mirror plate layers and the spacing of photochromatic layer mold are when closing film
0.8mm injects photochromic urethane composition, temperature is then raised to 35 DEG C from room temperature in 1h, then heat preservation 5.5h exists
3h is kept the temperature after being warming up to 65 DEG C in 5h, is warming up to 130 DEG C after being warming up to 105 DEG C in 0.5h after being then warming up to 95 DEG C in 0.5h,
Temperature is reduced to 75 DEG C in 1h after keeping the temperature 2h at this temperature；Be cleaned by ultrasonic after the completion of one-step solidification, then at 130 DEG C into
Row secondary curing 2.5h plates dura mater using dip coating, and vacuum evaporatation plates anti-reflection film, obtains color-changing lens.
Embodiment 7
A kind of color-changing lens, including mirror plate layers and photochromatic layer, preparation method include the following steps:
(1) 150g discoloration liquid, 200g dispersion resin and 4.9kg 2,5 (or 2,6)-bis- (isocyanatomethyls) is bicyclic
2.6kg tetra- (3- mercaptopropionic acid) Ji Wusi is added in the case where 12 DEG C, vacuum stirring after mixing at 12 DEG C in [2.2.1] heptane
Alcohol ester obtains the first mixed liquor；
(2) by 4.0g initiator and pungent two mercaptan of 2.1kg 4- thiopurine methyltransferase -3,6- dithia -1,8- vacuum stirring feelings
Condition mixes at 12 DEG C, obtains the second mixed liquor；
(3) the first mixed liquor and the second mixed liquor are mixed at 12 DEG C the case where being stirred under vacuum, then in -0.2MPa
Under the conditions of vacuumize and be filtered using the closed filter core of polytetrafluoroethylene (PTFE) that aperture is 1.2 μm after 55min, obtain photochromic
Urethane composition；
(4) by mirror plate layers and photochromatic layer mold clamping, mirror plate layers and the spacing of photochromatic layer mold are when closing film
0.9mm injects photochromic urethane composition, temperature is then raised to 35 DEG C from room temperature in 1h, then heat preservation 5.5h exists
3h is kept the temperature after being warming up to 65 DEG C in 5h, is warming up to 130 DEG C after being warming up to 105 DEG C in 0.5h after being then warming up to 95 DEG C in 0.5h,
Temperature is reduced to 75 DEG C in 1h after keeping the temperature 2h at this temperature；Be cleaned by ultrasonic after the completion of one-step solidification, then at 130 DEG C into
Row secondary curing 2.5h plates dura mater using dip coating, and vacuum evaporatation plates anti-reflection film, obtains color-changing lens.
Comparative example 1
Difference with embodiment 1 is only that, does not include dispersion resin in this comparative example.
Comparative example 2-3
Difference with embodiment 1 is only that, in this comparative example, the additive amount of dispersion resin be 150g (comparative example 2),
250g (comparative example 3).
Comparative example 4-5
Difference with embodiment 1 is only that, in this comparative example, the additive amount for the liquid that changes colour is 120g (comparative example 4), 280g
(comparative example 5).
Performance test
The embodiment 1-7 and comparative example 1-5 color-changing lens provided are tested for the property:
(1) ultravioletlight screening rate: using optical detector TM-3 test color-changing lens to the shielding rate of ultraviolet light；
(2) change colour it is whether uniform:, eyeglass is placed on white bottom plate, directly observe by human eye or sunlight irradiate under
The dimmed consistency of eyeglass background color is divided into excellent, good, uneven three grades；
(3) it qualification rate: is prepared using the preparation method that embodiment 1 provides, calculates product qualification rate.
Test result is shown in Table 1:
Table 1
| Sample | Ultravioletlight screening rate/% | Change colour uniformity | Qualification rate/% |
| Embodiment 1 | 94.0 | It is excellent | 96.0 |
| Embodiment 2 | 97.5 | It is excellent | 95.0 |
| Embodiment 3 | 97.0 | It is excellent | 95.0 |
| Embodiment 4 | 94.0 | It is good | 90.0 |
| Embodiment 5 | 94.0 | It is good | 93.0 |
| Embodiment 6 | 94.0 | It is good | 90.0 |
| Embodiment 7 | 94.0 | It is good | 90.0 |
| Comparative example 1 | 89.0 | Unevenly | 30.0 |
| Comparative example 2 | 94.0 | Unevenly | 65.0 |
| Comparative example 3 | 94.0 | Unevenly | 60.0 |
| Comparative example 4 | 90.0 | Unevenly | 70.0 |
| Comparative example 5 | 98.0 | Unevenly | 65.0 |
By embodiment and performance test it is found that the discoloration that photochromic urethane composition provided by the invention is prepared
Eyeglass is only 5-8% to the transmitance of ultraviolet light, it is possible to prevente effectively from filtering harmful ultraviolet light, protects eyesight well, and
And discoloration uniformity is good.By the comparison of embodiment 1 and comparative example 1 it is found that must include dispersion resin in composition of the invention,
Otherwise for discoloration liquid there are unstable, dispersion effect is poor, can not apply；By the comparison of embodiment 1 and comparative example 2-5 it is found that originally
Invent select photochromic urethane composition in discoloration liquid and dispersion resin should in range provided by the invention into
Row selection keeps performance more excellent.
The Applicant declares that the present invention is explained by the above embodiments photochromic urethane composition of the invention and its
Preparation method and application, the color-changing lens comprising it, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention
Above-described embodiment, which must be relied on, to be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of photochromic urethane composition, which is characterized in that the urethane composition includes as follows in parts by weight
Component:
2. photochromic urethane composition according to claim 1, which is characterized in that the discoloration liquid is at least two
The mixed liquor of color-change powder and isocyanates；
Preferably, the color-change powder is selected from spiro-pyrans class color-change powder, spiral shell uh piperazine class color-change powder or diarylethene color-change powder
In any one or at least two combination；
Preferably, the dispersion resin is polyol polyester, and further preferred polyadipate -1,6- hexylene glycol esterdiol gathers oneself
Diacid methyl-1,3-propanediol -1,6-HD esterdiol, polyadipate -1,4- butanediol neopentyl glycol esterdiol gather oneself two
Acid methyl -1,3- propylene glycol ester glycol, polyadipate methyl-1,3-propanediol ester -1,4- butyl glycol ester diol or poly- sebacic acid -
In 1,6- glycol neopentyl glycol esterdiol any one or at least two combination.
3. photochromic urethane composition according to claim 1 or 2, which is characterized in that the urethane raw is pressed
Parts by weight include following component:
Bicyclic [2.2.1] the heptane 480-530 parts by weight of 2,5 (or 2,6)-bis- (isocyanatomethyls)；
Four (3- mercaptopropionic acid) pentaerythritol ester 200-250 parts by weight；
The pungent two mercaptan 210-260 parts by weight of 4- thiopurine methyltransferase -3,6- dithia -1,8-.
4. photochromic urethane composition described in any one of -3 according to claim 1, which is characterized in that the initiation
The structural formula of agent is as follows:
RnSnX(4-n)；
Wherein, n is the integer of 1-4, and R is alkyl or aromatic radical, and X is-F ,-Cl or-Br.
5. the preparation method of photochromic urethane composition described in any one of -4, feature exist according to claim 1
In the preparation method includes the following steps:
(1) the discoloration liquid of formula ratio, dispersion resin are mixed with some polyurethanes raw material, obtains the first mixed liquor；
(2) initiator is mixed with remainder urethane raw, obtains the second mixed liquor；
(3) the first mixed liquor and the second mixed liquor are mixed, filtering, obtains the photochromic urethane composition；
Preferably, the preparation method includes the following steps:
(A) by the discoloration liquid of formula ratio, dispersion resin and 2,5 (or 2,6)-bis- (isocyanatomethyls) bicyclic [2.2.1] heptan
Four (3- mercaptopropionic acid) pentaerythritol esters are added after alkane mixing, obtain the first mixed liquor；
(B) initiator and pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- are mixed, obtains the second mixed liquor；
(C) the first mixed liquor and the second mixed liquor are mixed, filtering, obtains the photochromic urethane composition.
6. preparation method according to claim 5, which is characterized in that preparing the photochromic urethane composition mistake
Cheng Zhong, rate-determining steps (A)-(C) temperature independent is 10-15 DEG C；
Preferably, in step (A), four (3- mercaptopropionic acid) pentaerythritol esters are added under conditions of vacuum；
Preferably, step (B), (C) described mixing are to be stirred under vacuum mixing；
Preferably, before step (C) described filtering, 50-60min first is vacuumized under the conditions of-(0.1-0.2) MPa；
Preferably, step (C) filtering is carried out using the closed filter core of polytetrafluoroethylene (PTFE)；
Preferably, the aperture of the filter core is 0.8-1.2 μm.
7. preparation method according to claim 5 or 6, which is characterized in that the preparation method includes the following steps:
(A) by the discoloration liquid of formula ratio, dispersion resin and 2,5 (or 2,6)-bis- (isocyanatomethyls) bicyclic [2.2.1] heptan
Four (3- mercaptopropionic acid) pentaerythritol esters are added in the case where 10-15 DEG C, vacuum stirring after mixing at 10-15 DEG C in alkane, obtain
To the first mixed liquor；
(B) by initiator and pungent two mercaptan of 4- thiopurine methyltransferase -3,6- dithia -1,8- the case where being stirred under vacuum at 10-15 DEG C
Mixing, obtains the second mixed liquor；
(C) the first mixed liquor and the second mixed liquor are mixed at 10-15 DEG C the case where being stirred under vacuum, then in-(0.1-
0.2) it was carried out after vacuumizing 50-60min under the conditions of MPa using the closed filter core of polytetrafluoroethylene (PTFE) that aperture is 0.8-1.2 μm
Filter, obtains the photochromic urethane composition.
8. application of the photochromic urethane composition in light-sensitive sunglasses described in any one of -4 according to claim 1.
9. a kind of color-changing lens, which is characterized in that the color-changing lens include mirror plate layers and photochromatic layer；
Preferably, the raw material for preparing of the photochromatic layer includes photochromic poly- described in any one of claim 1-4
Urethane composition；
Preferably, the raw material for preparing of the photochromatic layer is photochromic poly- ammonia described in any one of claim 1-4
Ester composition；
Preferably, the photochromatic layer with a thickness of 0.8-1.0mm；
Preferably, the mirror plate layers are polyurethane mirror plate layers；
Preferably, the refractive index of the polyurethane mirror plate layers is 1.553-1.74.
10. the preparation method of color-changing lens according to claim 9, which is characterized in that the preparation method includes: by light
Mutagens chromatograph mold and mirror plate layers mold, photochromic urethane composition described in any one of injection claim 1-4,
Then solidify, obtain the color-changing lens；
Preferably, the diameter of the mirror plate layers is identical as the diameter of the photochromatic layer mold；
Preferably, the solidification carries out in the following manner:
One-step solidification is carried out first: temperature being raised to 30-35 DEG C from room temperature in 1h, then heat preservation 5-5.5h is warming up in 5h
3-3.5h is kept the temperature after 55-65 DEG C, is warming up in 0.5h after being warming up to 100-105 DEG C in 0.5h after being then warming up to 85-95 DEG C
120-130 DEG C, temperature is reduced to 65-75 DEG C in 1h after keeping the temperature 2-2.5h at this temperature；Ultrasound is clear after the completion of one-step solidification
It washes, secondary curing 2-2.5h is then carried out at 130 DEG C.
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